Treatment of textile materials



United States Patent 3,383,162 TREATMENT OF TEXTILE MATERIALS Robert E. Whitfield, Pleasant Hill, Allen G. Pittman, El Cerrito, and William L. Wasley, Berkeley, Calif., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Original application May 28, 1964, Ser. No. 371,150. Divided and this application May 12, 1967, Ser. No. 655,693

3'Clain1s. (Cl. 8-115.5)

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the World for all purposes of the United States Government, with the power to grant sub-licenses for such purposes, is hereby granted to the Government of the United States of America.

A principal object of this invention is the provision of new methods for treating fibrous materials, particularly textiles. Another object of the invention is the provision of the novel products so produced. Further objects and advantages of the invention will be obvious from the following description wherein parts and percentages are by weight unless otherwise specified. The symbol qb is used throughout to designate the structure In the process of fibrous materials, e.g., textiles, it is often desired to modify the inherent properties of the materials, for example, to improve their shrinkage characteristics, to increase their resistance to soiling, to enhance their softness, etc. Various procedures have been advocated for such purposes and they usually involve applying to the fibrous substrate an agent having the chemical structure required to effect the desired modification of the fibers. Such agents-which may be generically termed fiber-modifying agentsare generally polymers of any of various classes, for example, polyethylene, polypropylene, or other polyolefines; chlorosulphonated polyethylenes; polyvinylpyrrolidones; polyepoxides; formaldehyde-melamine resins; vinyl polymers; starch and starch derivatives, etc. Ordinarily, application of the polymer with nothing more yields at best a temporary efiect; the polymer is removed when the treated fibers are subjected to laundering or dry cleaning. To attain a more lasting effect, it is conventional to apply the polymer in conjunction with an agent-commonly termed a fixative or curing agentin order to cause a cross-linking of the molecules of the polymer rendering it insoluble in water and dry-cleaning solvents. A universal feature of such procedures is that they require a curing operation at elevated temperatures to attain the desired insolubilization of the polymer. A typical procedure of this type is disclosed by Bruner et a1. (Patent No. 2,678,286) who apply a solution containing (a) chlorosulphonated polyethylene and (b) a fixative such as hexamethylenediamine or 3-methoxyhexamethylene diamine to wool and then cure the treated wool at 150 C. for anywhere from 2 to 10 minutes. Such heat curing steps entail serious disadvantages. For one thing, they impede production by tying up large amounts of material. For example, in textile mills processing is conducted at rates of at least 25 yards per minute and it is obvious that if a heat cure of 10 minutes is required, 250 yards of material will constantly be tied up in the curing oven, hence not available for use or sale. Other disadvantages are the expense of the heating equipment, maintenance of the auxiliary devices such as guides, rollers, etc. and the cost of fuel. A further point is that heating at curing temperatures often is detrimental to the fibrous material, causing such deleterious changes as yellowing, loss in tensile strength and abrasion resistance, and other changes attributable to degradation of the fiber molecules. Wool is a typical example of a fiber which is readily yellowed and degraded by exposure to elevated temperatures, particularly when in contact with alkaline substances, e.g., curing agents containing amino groups.

A particular feature of the present invention is that essentially permanent modifications of fiber properties are attained without any heat-curing step. As a result, the invention yields the advantages of rapid and simple operation, decreased cost of production, and avoidance of fiber yellowing and degradation.

In accordance with the invention, the properties of a fibrous substrate are modified by applying thereto a preformed polymer and cross-linking it to form a three-dimensional structure, the cross-linking being accomplished by reaction of the pre-formed polymer and the fixative at a phase boundary. In a typical embodiment of the invention, wool is first impregnated with an aqueous solution of the fixative, e.g., a diamine such as hexamethylene diamine. The wool is then impregnated with a solution of a pre-formed polymer in a water-immiscible solvent such as carbon tetrachloride. The polymer may be, for example, a copolymer of ethylene and methacryloyl chloride, containing at least three COCl groups per molecule. By serial application of these solutions to the fabric, each fibrous element is coated with a two-phase system, for example, an inner layer of diamine in water and an outer layer of the highly reactive polymer in water-immiscible solvent. Under these conditions, the diamine and the polymer react almost instantaneously at the boundary between the phases, producing in situ on the fiber a crosslinked, insoluble, resin coating. By suitable selection of the complementary reactants, a wide variety of polymeric, fiber-modifying agents can be cross-linked in situ on fibers. It is to be particularly noted that no heat-curing step is neededthe serial application of the reactants is all that is necessary. The critical feature in this regard is that we provide a phase boundary-limited system whereby the cross-linking takes place directlyas soon as the reactants are appliedand hence there is no need for heat curing to promote the reaction.

In the patents of Miller et a1. 3,078,138 and Whitfield et al. 3,079,216, 3,079,217, 3,084,018, 3,084,019, and 3,093,441 there are disclosed processes wherein linear condensation polymers-sag. polyamides--are formed in situ on fibrous substrates by polymerizing complementary bifunctional polymer intermediates in an interfacial system. Thus in a typical embodiment thereof, wool is first impregnated with an aqueous solution of a diamine and then impregnated with a solution of a diacid chloride in a water-immiscible solvent such as carbon tetrachloride. Under these conditions, polymerization takes place at the interface between the mutually-immiscible phases, producing in situ a linear polyamide.

Although the procedures of the aforesaid patents provide very useful and practical results and are indeed in commercial use, they inherently possess certain limitations. The procedure of the present invention does not have these limitations and, moreover, provides results not obtainable by the prior techniques. These points are further explained as follows:

(1) A fundamental item is that the patened procedure utilizes an interfacial system to build a polymer from small units so that the procedure may accurately be termed interfacial polymerization and is so referred to hereinafter. On the other hand, the present procedure starts with a pre-formed polymer and utilizes an interfacial system to cross-link it. Thus, the present procedure may be considered as involving interfacial cross-linking of a pre-formed polymer. The distinction is not just a matter of words but involves basic and important distinctions. A vital point is that the patented system forms linear polymers. Bifunctional polymer-forming monomers are applied and a linear polymer is produced on the surface of the substrate. In contrast, in the present procedure a pre-formed linear polymer is initially applied as the primary reactant. The reaction which then occurs at the phase boundary is a cross-linking of this pre-formed polymer; that is, individual molecules of the original polymer are joined to another, forming a three-dimensional structure.

These distinctions are further demonstrated by the following illustrative formulas:

(a) Interracial polymerization:

Hex Seb hexamethylene sebacoyl Linear polymer containing diamine c oride alternating units derived from hexamethylene diamine and sebacoyl chloride (b) In accordance with the invention:

fer such attributes as enhanced resiliency; polystyrene polymers to confer stiffness; perfluoroacrylates to provide resistance to soiling; etc. It is important to note at this point that addition polymers cannot be formed by the aforesaid interfacial polymerization technique; monomers required to form addition polymers will not polymerize under the conditions in question at any practical rate.

(3) In the interfacial polymerization system, permanency of fiber modification is attained only if the polymer Hex Seh Hex Seb Hex Seh Hex Seb Hex : MEEEEEEMEEEEEEMEEEEEE Hex Hex ..:..MEEEEEEII'IEEEEEEMEEEEEE Since linear polymers contain independent chains, whereas cross-linked polymers contain interconnected chains, substantial distinctions in properties are displayed by the two forms of polymers. For example, linear polymers are soluble in organic solvents; they are fusible and display typical thermoplastic properties, i.e., they flow when heated. Cross-linked (thermosetting) polymers are insoluble in organic solvents and at most are swelled thereby. Also, they are not fusible and do not exhibit plastic properties when heated, i.e., they do not flow.

(2) The interfacial polymerization system is limited to the formation of condensation polymers, i.e., polyamides, polyurethanes, polyureas, polyesters, polycarbonates, and interpolymers containing various combinations of amide, urethane, urea, ester, or carbonate groups. In contrast, the procedure of the present invention is not so limited. One can apply all kinds of polymersnot only condensation polymers but also addition polymers. As a matter of fact, the present invention is of particular advantage for the very reason that one can apply addition polymers, for example, polyolefines, polyacrylates, polyperfiuoroacrylates, polyvinyls, and the like. Addition polymers have the benefits that they are readily available, relatively inexpensive, and, most importantly, offer a very wide spectrum of physical and chemical properties for the modification of the fibrous substrate. This last item is illustrated by the following examples: Application of elastomers such as chlorosulphonated polyethylene to conlinked through hexaniethylene diamine units becomes grafted to the fiber molecules. If the characteristics of the substrate are such that no grafting occurs, the polymer deposit is but temporary and is removed by such influences as laundering, dry-cleaning, mild abrasion, etc. However, in the process of the present invention grafting is not an essential factor. Permanence of modification depends on the fact that the applied polymer is crosslinked (by reaction with the fixative) to form a polymer which is 3-dimensional, hence inherently insoluble. Moreover, if grafting does occur, one attains a double-anchoring effect in that both the grafting and the cross-linking contribute to the permanence of the fiber modification. To sum up the situation, grafting is essential in the prior procedure where permanence of modification is required. In accordance with the present invention, permanence of fiber modification is attained by cross-linking a pre-formed polymer. Grafting, if it does occur, serves to reinforce the durability of the modification.

(4) Another item is that the interfacial polymerization procedure by its very nature yields polymers wherein polar groups (amide, urea, urethane, ester or carbonate groups) recur along the polymer chain in relatively close spacing. For example, polyhexamethylene sebacamide (produced by polymerizing hexamethylene diamine and sebacoyl chloride in situ on a fibrous substrate) will contain an amide group recurring after each group of 6 or 8 carbon atoms. Such polarity may be undesirable, for example, in instances where it is intended that the treated fibers display a high degree of hydrophobicity. On the contrary, the process of the present invention does not necessarily yield such highly polar products and, in fact, one can readily form crosslinked polymers which contain very lengthy chains completely free from polar radicals. Typically, this can be done by applying a polymer containing long hydrocarbon chains such as those of polyethylene, polypropylene, polybutylene, etc. The resulting cross-linked polymer will contain very long carbon chains between polar groups; indeed, these carbon chains may contain anywhere from 25 or 50 to hundreds of carbon atoms.

COMPONENT A.(THE PRE-FORMED POLYMER) In the practice of the invention, selection is made of the appropriate complementary agents to provide the desired modification of the fibers. These complementary agents will comprise a preformed polymer (hereinafter termed Component A) and the fixative or cross-linking agent (hereinafter termed Component B).

As noted hereinabove, the invention is of wide versatility and a multitude of different substances may be used as Component A. Basically, Component A may be any polymer which contains highly reactive groups and which is soluble in water or in organic solvents such as alcohol, acetone, hydrocarbons, or chlorinated hydrocarbons, etc. From a structural viewpoint, Component A is a linear polymer, with or without branching, which possesses the above critical characteristics. It is preferred that Component A have a molecular weight of at least 1000 to provide adequate film-forming and fiber-modifying ability. The characteristic of solubility is desired so that the polymer can be uniformly applied to fibrous substrates in the form of a solution. The highly reactive groups are required to provide the sites for the eventual cross-linking of Component A in the phase boundary system. The expression highly reactive group is employed herein to designate a functional radical which on contact with a complementary functional radical under interfacial conditions will combine therewith rapidly and directly without requiring any after-treatments such as oven cures. Because of the facility with which these groups react on contact, they may also be termed contact-responsive or contact-effective functional groups. It is essential that there be at least two, preferably at least three, of these highly reactive groups per polymer molecule. For best results it is preferred that the number of highly reactive groups be correlated with molecular weight of the polymer, employing a greater number as the polymer molecular weight is increased. Illustrative examples of highly reactive groups which may be present are carbonyl halide (COX); sulphonyl halide (SO X); haloformate (OCOX); carbamyl halide (NHCOX); isocyanate (NCO);

and hydroxy (OH). In the above formulas X stands for a halogen, i.e., fluorine, chlorine, bromine, or iodine. The sulphur analogues of any of the above oxygencontaining species, e.g., CSCl, SCOCl, SCSC1, -OCSCl, NCS, SH, etc., are also included within the ambit of the invention. The several highly reactive groups of Component A may be all the same or may be of different species. For example, the reactive groups may be two or more carbonyl chloride groups; two or more sulphonyl chloride groups; two or more amine groups; one carbonyl chloride group and one or more sulphonyl chloride groups; one amino group and one or more hydroxyl groups; one chloroformate group and one or more carbonyl chloride groups; etc. Other combinations of-two or more different species of reactive groups will be evident from the above.

The expression acid halide group is used herein as generic to carbonyl halide, sulphonyl halide, haloformate, and carbamyl halide groups.

Illustrative types of polymers which may be employed as Component A are given below:

COMPONENT A.-(ADDITION POLYMERS) Basically, this embodiment of Component A may be considered as an addition polymer which contains pendant highly reactive groups of the types described above. Typically, these substances are prepared by copolymerizing two types of unsaturated monomeric materials, namely, a first ingredient used in major proportion (e.g., about 55 to mole percent of the copolymerization system) and a second ingredient used in minor proportion (about 5 to 45 mole percent of the copolymerization system). Generally, the first ingredient is provided to contribute to the copolymer the desired high molecular Weight and also to contribute to the polymer the ultimate properties desired to be imparted to the fibrous substrate in the cross-linking procedure. The second ingredient pro vides the pendant, highly reactive groups.

Typical examples of monomers which may be used as the major ingredient are:

Alkyl esters of acrylic acid and alkyl esters of any of the various ot-alkylacrylic or u-haloacrylic acids, e.g., the methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclohexyl, oleyl, etc., esters of acrylic, methacrylic, ethacrylic, propacrylic, chloroacrylic, bromoacrylic, etc. acids.

Aryl and aralkyl esters of acrylic acid or the a-substituted acrylic acids, e.g., phenyl, 0-, m-, p-tolyl, dodecylphenyl, benzyl, phenylethyl, etc., esters of acrylic, methacrylic, ethacrylic, propacrylic, chloroacrylic, bromoacrylic, etc. acids.

Alkyl acrylates or methacrylates containing an oxygen bridge, typically methoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, octoxyethyl acrylate, cyclohexoxyethyl acrylate, benzoxyethyl acrylate, phenoxyethyl acrylate, methoxyethyl methacrylate, phenoxyethyl methacrylate, et

Acrylates containing such radicals as thioether, sulphone, or sulphoxide, for example, the esters of acrylic acid or methacrylic acid with alcohols of the types:

wherein R is an alkyl radical such as methyl, ethyl, propyl, butyl, etc., or an aryl or aralkyl radical such as phenyl, tolyl, benzyl, phenylethyl, etc.

Vinyl esters of fatty acids, e.g., vinyl acetate, propionate, butyrate, valerate, caprylate, caprate, laurate, myristate, palmitate, stearate, oleate, etc.

Allyl and methallyl esters of fatty acids, e.g., allyl and methallyl acetates, propionates, butyrates, valerates, caprylates, caprates, laurates, myristates, palrnitates, stearates, oleates, etc.

N-dialkyl acrylamides and N-dialkyl a-substituted acrylamides, for example, N-dimethyl, N-diethyl, N-dipropyl, N-dibutyl, N-diamyl, N-dihexyl, N-dioctyl, N-didodecyl, etc., acrylamides, methacrylamides, ethacrylamides, propacrylamides, etc.

Olefinic hydrocarbons and halogenated olefinic hydrocarbons such as ethylene, propylene, butylene, isoprene, butadiene, styrene, chloroprene, a-methylstyrene, dimethylstyrene, vinyl naphthalene, dichlorostyrenes, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, vinyl fluoride, etc.

Ketones such as methyl vinyl ketone, ethyl vinyl ketone, isopropyl vinyl ketone and other alkyl vinyl ketones, methyl isopropyl ketone, methyl alkyl ketone, etc.

Itaconic diesters, for example, the dimethyl, diethyl diisopropyl, dibutyl, dihexyl, didodecyl, and other dialkyl esters of itaconic acids. Diaryl and diaralkyl esters of itaconic acid, e.g., diphenyl itaconate, dibenzyl itaconate, di-(phenylethyl) itaconate, etc.

Other compounds containing the typical CH C grouping such as cyanostyrenes, vinyl thiophene, vinyl pyridine, vinyl pyrrole, acrylonitrile, methacrylonitrile, alkyl vinyl sulphones such as ethyl vinyl sulphone. Compounds of the types:

where R is H or CH and wherein R is a lower alkyl group such as CH C H etc.

Vinyl ethers, for example, monomers of the type wherein R is an alkyl radical such as methyl, ethyl, propyl, butyl, benzyl, etc.

In many cases, it is preferred that the major ingredient be a fluorine-containing monomer. Copolymers produced therefrom are useful to impart such characteristics to the fibrous substrates as resistance to both oiland waterborne soils. Typical illustrative examples of fluorine-containing monomers are: perfluoro-t-butyl acrylate, perfiuoro-t-butyl methacrylate, and esters of the type II(CFzCF )nCH2-OC( 3=CHz wherein R is H or CH, and n is an integer from 2 to 6. Typical examples of this type of primary perfiuoroalkyl ester are: 1,1,5 trihydroperfluoropentyl acrylate and methacrylate, 1,i,7-trihydroperfluoroheptyl acrylate and methacrylate, 1,1,9-trihydroperfluorononyl acrylate and methacrylate, 1,1,11 trihydroperfiuoroundecyl acrylate and methacrylate, 1,1,13-trihydroperfluorotridecyl acrylate and rnethacrylate, etc. Usually, it is preferred that the fiuoroalkyl radical contain at least 3 fluorine atoms and an especially desirable type of fiuoroalkyl ester for the multi-purpose treatment mentioned above is one wherein the fiuoroalkyl radical not only contains at least 3 fluorine atoms but also has its omega carbon atom completely fluorinated. Typical of these particularly preferred fiuoroalkyl esters are those of the type wherein R is H or CH, and n is an integer from 0 to 18. Illustrative examples of such compounds are the acrylic and methacrylic acid esters of: 1,1-dihydroperfluoropropyl alcohol, 1,1-dihydroperfiuorobutyl alcohol, 1,1-dihydroperfiuorohexyl alcohol, 1,1-dihydroperfluorooctyl a1- cohol, 1,1-dihydroperfluorodecyl alcohol, 1,1-dihydroperfluorododecyl alcohol, 1,1-dihydroperfluorohexadecyl alcohol, 1,l-dihydropertluorooctadecyl alcohol, etc.

Another useful type of fluorine-containing monomer comprises the compounds of the structure 1'! g R RrSOzN-CC=OHz wherein R; is a saturated fluorocarbon structure containing from 4 to 18 fully fluorinated carbon atom, R is hydrogen or an alkyl group containing from 1 to 6 carbon atoms and R" is hydrogen or a methyl group. Typical examples of particular compounds in this area are: N- methyl, N-perfluorobutanesulfonyl acrylamide; N-methyl, N peifiuorobutanesulfonyl methacrylamide; N perfiuoro(Z-methylcyclohexane)sulfonyl methacrylamide; N- methyl, N perfiuoro(4 methylcyclohexane)sulfonyl acylamide; N-prop'yl, N-perfiuoro(Z-rnethylcyclOhexane)- sulfonyl methacrylamide; N-perfiuorooctanesulfonyl acrylamide; N-perfiuorooctanesulfonyl methacrylamidc; N- ethyl, N-perfluorooctanesulfonyl acrylamide; N-isobutyl, N-perfluoro(4-ethylcyclohexane sulfonyl acrylamide; N- isobutyl, N-perfiuorodecanesulfonyl methacrylamide; N- propyl, N-perfluorododecanesulfonyl acrylamide; N-(nhexyl), N-perfluoroctadecanesulfonyl acrylamide.

In cases where it is desired to impart water repellency to the fibrous substrate, one may employ as the major ingredient unsaturated monomers containing silicon. Typical in this category are the acryloxymethyl (or methacryloxymethyl) derivatives of organic silanes or polysiloxanes, for example, compounds of the types R R R wherein R is hydrogen or methyl and the R"s are monovalent organic radicals, typically alkyl groups containing 1 to 18 carbon atoms, cyclohexyl, phenyl, toluyl, benzyl, diphenyl, or the like. Typical examples of compounds in this category are acryloxymethyl trimethylsilane, methacryloxymethyl trimethylsilane, acryloxymethyl dimethylphenylsilane, methacryloxymethyl dimethylphenylsilane, acryloxymethyl pentamethyldisiloxane, rnethacryloxymethyl pentamethyldisiloxane, etc.

Illustrative examples of the minor ingredient are as follows:

(1) Unsaturated monomers containing a carbonyl halide group. e.g., compounds of the formula i ClIz O-CX wherein R is hydrogen, an alkyl group such as methyl, ethyl, propyl, butyl, phenyl, etc. and wherein X is Cl, Br, F or I.

Styrene derivatives of the type t OH2=C-COX wherein X and R are as defined above.

(2) Unsaturated monomers containing a sulphonyl halide group, e.g., compounds of the formulae CHz=C-SOzX wherein R and X are as defined in (1) above.

(3) Unsaturated monomers containing carboxylic acid or sulphonic acid groups, for example R CH2=(JCOOH R CIIz=( ]-SO3:\I

R OH;=(3OOOM f CHFC-SOQI\I wherein R is as defined in (1) above and wherein M is H or an alkali metal.

Copolymers made with these sulphonicor carboxyliccontaining monomers may be converted to the corresponding acid halide forms by, for example, reaction with a thionyl halide, phosphorus trichloride, or the like.

(4) Unsaturated monomers containing an isocyanate or isothiocyanate group, for example, compounds of the types i CHFC-NCY f CHFC-CHz-NCY OHFONHR wherein R is as defined in (1) above and R is as defined in (4) above.

(7) Unsaturated monomers containing a haloformate or carbamyl halide group, for example wherein R and X are as defined in (1) above and wherein R is as defined in (4) above.

COMPONENT A.-(CONVERTED ADDITION POLYMERS) If desired, one may prepare addition polymers essentially free from highly reactive groups and then subject them to known reactions to introduce the necessary highly reactive groups. An example in this area is the chlorosulphonation of polyolefines such as polyethylene or polypropylene by reaction with S0 and C1 This introduces chloro groups and sul-phonyl chloride SO C-l) groups into the polymer. Another example is the partial hydroiysis of vinyl ester or vinyl ether polymers, to introduce hydroxyl groups into the polymer chain. Another example is a copolymer containing carboxy groups which are then converted into carbonyl halide groups by reacting the copolymer with such agents as thionyl chloride, phosphorus trichl-oride, or the like.

COMPONENT A.(CONDENSATIO'N POLYMERS) Component A need not necessarily be an addition polymer; one may use condensation polymers of all types. Although some investigators employ the term condensation polymer only in respect to polymers wherein a low molecular weight by-product (such as H O or HCl) is split out during polymer formation, we employ the term in the broader and accepted sense as designating any polymer which contains inter-unit functional groups not present in the monomers. Thus, we include such types as polyalkyleneimines, polyurethanes, polyureas, etc., whose formation is not ordinarily accompanied by any byproduct elimination. Various types of condensation polymers which may be used in the practice of the invention are listed in the following paragraphs by way of illustration but not limitation.

COMPONENT A.(POLYALKYLENE IMINES) A useful class of polymers which can be used as Component A are the polyyalkylene imines. A special feature of these is that they have built-in reactive groups on the polymer backbone, namely, internal imine (-NH-) groups and terminal amine NH groups. Typical examples are the polymers of ethylene imine, propylene imine, 1,2-butylene imine, 2,3-butylene imine, 2,2-dimetl1- yl ethylene imine, 2,2,3-trimethyl ethylene imine, 2,2-dimethyl-3-propyl ethylene imine, cyclohexyl ethylene imine, phenyl ethylene imine, etc. These compounds, as Well known in the art, can be prepared, for example, by polymerizing the alkylene imine monomers in the presence of a catalyst such as sodium bisulphite, hydrochloric acid, sulphuric acid, acetic acid, hydrogen peroxide, etc. Generally, it is preferred to use the polyalkylene imines which can at least be partially soluble in Water.

COMPONENT A.'(POLYESTERS) Polyesters derived from polyols such as ethylene glycol, propylene glycol, trimethylene glycol, hexa-methylene glycol, glycerol, pentaerythritol, sorbitol, trimethylolpropane, etc., and dibasic acids such as succinic, adipic, sebacic, phthalic, terephthalic, hexahydrophthalic, maleic, and the like. By suitable adjustment of the proportions of reactants in known manner, the polyesters will contain free hydroxy groups. The resulting polyesters can be employed directly as Component A, utilizing the free hydroxy groups as the highly reactive groups. Another plan is to react the 'hydroxylated polyethers with a diacid chloride (or bischloroformate) to provide a polyether containing free carbonyl chloride (or chlorofo-rrnate groups). In this connection, typical reactants are succinyl chloride, adipyl chloride, pimelyl chloride, sebacyl chloride, pht-halyl chloride, ethylene glycol bischloroformate, diethylene glycol bischloroforma-te, hexane-1,6-diol bischloroformate, and the like. As well known in the art, the polyester and diacid chloride (or bisch'loroform'ate) are employed in such proportion as to provide a CO'Cl/OH (or OCOCl/OH) ratio of more than one to one whereby to ensure that the product contains free carbonyl chloride or chloroformate groups. In a preferred form of the invention, one uses polyesters containing free isocyanate groups. Such polymers can be readily prepared by reacting the hydroxylated polyester wit-h a diisocyanate. Typical examples of the diisocyanates are 0-, m-, or p-phenylene diis-ocyanate, toluene 2,4- or 2,6-) diisocyanate, metaxylylene diisocyanate, 3,4,3',5'-bixylylene-4,4'-diisocyanate, etc. As well known in the art, the diisocyanate and polyester are employed in such proportion as to provide an NCO/OH ratio of more than one to one whereby to ensure that the product contains free NCO groups. Products of this type are sometimes referred to in the art as polyurethanes because they contain internal urethane 1 1 groups, formed through combination of hydroxy groups of, the polyester with isocyanate groups of the diisocyanate reactant.

COMPONENT A. (POLYETHERS) Polyethers derived, for example, by polymerizing an oxide (or epoxide, as they are often termed) with a polyhydric alcohol such as ethylene glycol, propylene glycol, trimethylene glycol, glycerol, pentaerythritol, sorbitol, trimethylolpropane, etc. Generally, the polyethers are derived from the simple alkylene oxides such as ethylene oxide or propylene oxide but one may also use such compounds butylene oxide,

isobutylene oxide,

trimethylethylene oxide,

dodecylene oxide,

hexadecylene oxide,

tetramethylethylene oxide,

u-rnethylstyrene oxide,

styrene oxide,

cyclopentene epoxide,

cyclohexene epoxide,

vinyl cyclohexene epoxide,

butadiene monoepoxide,

naphthyl ethylene oxide,

dipentene epoxide,

1,2-epoxy-2,4,4-trimethyl pentane (diisobutylene epoxide),

1,1-diphenylethylene oxide,

epichlorhydrin,

epibromhydrin,

1,1,l-trifiuoro-Z-propylene oxide,

1,1,l-tritluoro-l-methyl-Z-propylene oxide,

1,1,1-trifiuoro-2-butene oxide,

1,1,l,2,2,3,3-heptafluoro-4 hexene oxide,

hexylglycidyl ether,

'allylglycidyl ether,

phenylglycidyl ether,

2-chloroethylglycidyl ether,

o-chlorophenylglycidy-l ether,

methacrylchloride epoxide,

3-chloro-l,2-epoxybutane glycidol,

methyl 9,10-epoxystearate,

3,4-epoxycyclohexyl cyanide,

2-methyl-2,3-epoxyhexanol, etc.

The resulting polyethers can be employed directly as Component A, utilizing the free hydroxy groups as the highly reactive groups. In such case, it is preferred that the polyethers contain at least 3 hydroxy groups per molecule, obtainable by utilizing a polyhydric alcohol containing at least 3 hydroxy groups in the polymerization with the oxide monomer. Another plan is to react the hydroxylated polyether with a diacid chloride (or bischloroformate) to provide a polyether containing free carbonyl chloride (or chloroformate groups). In this connection, typical reactants are succinyl chloride, pimelyl chloride, sebacyl chloride, phthaly-l chloride, ethylene glycol bischloroformate, diethylene glycol bischloroformate, hexane-1,6-diol bisch'loroformate, and the like. As well known in the art, the polyether and diacid chloride (or bischloroformate) are employed in such proportions as to furnish a COCl/ OH (or OCOCl/OH) ratio of more than one to one whereby to ensure that the product contains free carbonyl chloride or chloroformate groups. In a preferred form of the invention, one uses polyethers containing free isocyanate groups. Such polymers can be readily prepared by reacting the hydroxylated polyether with a diisocyanate. Typical examples of the diisocyanates which may be reacted with the polyethers are m-, or p-phenylene diisocyanates, toluene 2,4- (or 2,6-) diisocyanate, metaxylylene diisocyanate, 3,5,3,5-bixy-lylene-4,4-diisocyanate, 3,3'-bitolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, etc. As well known in the art, the diisocyanate and polyether are employed in such proportions as to provide an NCO/ OH ratio of more than one to one whereby to ensure that the product contains free isocyanate groups. These products are sometimes referred to as polyurethanes because they contain internal urethane groups, formed through the combination of hydroxy groups of the polyether with isocyanate groups of the diisocyanate reactant.

COMPONENT A.( POLYAMIDES) The polyamides used in accordance with the invention are those derived from polyamines and polybasic acids. Methods of preparing these polyamides by condensation of polyamines and polycarboxylic acids are well known in the art and need not be described here. One may prepare polyamides containing free amino groups or free carboxylic acid groups. Generally, it is preferred to employ polyamides which contain -free amino groups. The polyamides may be derived from such polyamines as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, 1,4-diamino butane, 1,3-diaminobutane, hexamethylene diamine, 3-(N-isopropylamino) propylamine, 3, 3-imino-bispropylamine, and the like. Typical polycarboxylic acids which may be condensed with the polyamines to form polyamides are glutaric acid, adipic acid, pime'lic acid, suberic acid, aze-laic acid, scbacic acid, isophthalic acid, tereph-thalic acid, betamethyl adipic acid, 1,2-cycl0- hexane dicarboxylic acid, malonic acid, polymerized fat acids, and the like. Depending on the amine and acid constituents and conditions of condensation, the polyamides may have molecular weights varying about from 1,000 to 10,000 and melting points about from 20-200 C. Particularly preferred for the purpose of the invention are the polyamides derived from aliphatic polyamines and polymeric fat acids. Such products are disclosed, for example, by Cowan et al. Patent No. 2,450,940. Typical of these polyamides are those made by condensing ethylene diamine or diethylene triamine with polymeric fat acids produced from the polymerization of drying or semi-dry ing oils, or the free acids, or simple aliphatic alcohol esters of such acids. The polymeric fat acids may typically be derived from such oils as soybean, linseed, tung, perilla, oiticica, cottonseed, corn, tall, sunflower, safflower, and the like. As well known in the art, in the polymerization the unsaturated fat acids combine to produce a mixture of dibasic and higher polymeric acids. Usually the mixture contains a preponderant proportion of dimeric acids with lesser amounts of trimeric and higher polymeric acids, and some residual monomeric acid. Particularly preferred are the polyamides of low melting point (about 20-90 C.) containing free amino groups which may be produced by heating together an aliphatic polyamine, such as diethylene triamine, triethylene, tetramine, 1,4-diaminobutane, tetraethylene pentamine, 1,3-diaminobutane, and the like, with the polymerized fat acids. Typical among these is a polyamide derived from diethylene triamine and dimerized soybean fatty acids.

COMPONENT A.(OTHER CONDENSATION TYPES) A useful class of condensation polymers, particularly where it is desired to impart such qualities as shrink resistance, water repellency, resistance to water-borne soils, etc., are the polysi'loxanes. Typical are the polymers containing a multiplicity of siloxane units of the structure wherein R, R, and Q are as above. The polymers or copolymers maybe modified to introduce selected highly reactive groups. For example, polymers or copolymers containing free OH or NH, groups may be reacted with an excess of a diisocyanate, such as toluene diisocyanate, to provide a siloxane with free isocyanate groups.

Similarly, polymers or copolymers containing free OH or NH groups may be reacted with an excess of a diacid chloride or a bischlorofiormate-for example, adipoyl chloride or ethylene glycol bischloroformate-Jo produce a siloxane containing free carbonyl chloride or chloroformate groups.

Other classes of condensation polymers usable as Component A are: Polymers containing free amine or isocyanate groups. prepared by copolymerizing a diamine such as hexamethylene diamine with a diisocyan-ate such as toluene diisocyanate. Polycarbonates containing free hydroxy or chloroformate groups, prepared by copolymerizing a polyol such as bisphenol A with ethylene glycol bischlorof-ormate. Polycarbonates containing free hydroxy groups may be reacted with diisocyanates, as described hereinabove in connection with the polyesters, to provide a polycarbonate containing free isocyanate groups.

COMPONENT B.-(THE FIXATIVE) Component B may be any compound containing at least two highly reactive groups. As to these groups, the same choice is available as set forth hereinabove in connection with Component A and thus they may typically be of the following types: Carbonyl halide (COX), sulphonyl halide (-SO X), haloformate (OCOX), carbamyl halide (-NHCOX) amine (NH imine (NH), hydroxy (O-H), isocyanate (NCO). In the above formulas X stands for F, Cl, Br, or I. The sulphur analogues of any of the above oxygen-containing species, e.g., CSCl, SCOCl, SCSC1, OCSCl, NCS, SH, etc., are also included within the ambit of the invention.

The several reactive groups of Component B may be all of the same species or of different species. For example, the reactive groups may be two or more carbonyl chloride groups; two or more sulphonyl chloride groups; two or more amine groups; one carbonyl chloride group and one or more sulphonyl chloride groups; one amine group and one or more hydroxyl groups; etc. Other combinations of two or more different species of reactive groups will be evident from the above illustrations.

It is, of course, obvious that in a practice of the invention one selects Components A and B so that they contain reactive groups which are in a complementary relation, that is, which are reactive with one another, whereby the desired cross-linking will take place. The following table illustrates how one may select the reactive groups on the respective Components A and B to ensure that they are in complementary (reactive) relationship:

COMPLEMENTARY REACTIVE GROUPS Reactive group on one component (A or B) Complementary reactive group on complementary component (B or A) Carbonyl halide Amine, imine, hydroxy. sulphonyl halide. Do. Halotormate Do.

We generally prefer to employ systems wherein one component carries carbonyl halide, haloformate, or isocyanate groups and the other component carries groups containing active hydrogen atoms, i.e., hydroxy, amine, or imine groups. Of these, amine and imine groups are particularly preferred as providing especially rapid cross-linking. System with isocyanates and amines (or imines) offer the special benefit that the cross-linking does not produce any by-products, e.g no hydrogen halide as in the acid halide-amine systems.

Since the goal of the phase boundary-limited reaction is to cross-link the preformed polymer (Component A), it is necessary that each of the Components A and B contain at least two reactive groups and, moreover, that the sum of the groups be five or more. For example, if the selected Component A contains two of the highly reactive groups, Component B should contain no less than three of the complementary reactive groups. If the selected Component A contains three of the reactive groups, it is evident that Component B may contain as few as two of the complementary groups. Moreover, as the molecular weight of Component A is increased, it is preferred that the sum of the reactive groups be more than five to assure the proximity of complementary reactive groups during the cross-linking reaction.

Illustrative examples of compounds which may be used as Component B are listed below:

COMPONENT B.(FIXATIVE) CONTAINING COX GROUPS Typically, one may employ compounds of the aliphatic, aromatic, or heterocyclic series containing at least two carbonyl halide (COX) groups. The compounds may be substituted if desired with non-interfering (non-functional) substituents such as ether groups, thioether groups, sulp'hone groups, etc. Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: Phosgene, oxalyl chloride, maleyl chloride, fumaryl chloride, mal-onyl chloride, succinyl chloride, glutaryl chloride, adipyl chloride, pimelyl chloride, suberyl chloride, azelayl chloride, seba-cyl chloride, cyclohexane-l,4-biscarbonyl chloride, phthalyl chloride, isophth-alyl chloride, terephthalyl chloride, 4,4'-biphenyl dicarbonyl chloride, fl-hydromuconyl chloride, i.e.,

diglycollic acid chloride, i.e., O(CH -COCl) higher homologues of this compound as O(OH CH COCl) dithiodigylcolli-c acid chloride, diphenylolpropanediacetic acid chloride, i.e. (CH C(C H OCH COCI) trimellityl chloride, i.e., C H (COCI) and the like. If desired, mixtures of diiferent carbonyl halides may be used. It is also evident that the sulphur analogues of these compounds may be used and are included within the spirit of the invention. Thus, instead of using compounds containing two -COCl groups one may use compounds containing one -CSC1 and one COCl group or compounds containing two -CSCl groups. Moreover, although the carbonyl chlorides are preferred as they are reactive and relatively inexpensive, the corresponding fluorides, bromides, and iodides may be used.

It is generally preferred to use the aliphatic compounds containing two carbonylchloride groups in alpha, omega positions, particularly those of the type:

ClCO(CH COCl wherein n has a value from 2 to 12. Another preferred category includes the compounds of the formula (where A is the benzene o-r cyclohexane radical), especially para-substituted compounds such as terephthalyl and hexahydroterephthalyl chlorides.

COMPONENT B.(FIXATIVE) CONTAINING SO X GROUPS Typically, one may employ compounds of the aliphatic, aromatic, and heterocyclic series containing at least two sulphonyl halide (-SO X) groups. The compounds may be substituted if desired with non-interfering (non-functional) groups such as ether groups, thioether groups, sulphone groups, etc. Typical compounds in this category are listed below by way of illustration and not limitation: benzene-1,3-disulphonyl chloride, benzene-1,4-disulphonyl chloride, naphthalene-1,5-disulphonyl chloride, naphtha- 1ene-2,7-disulphonyl chloride, biphenyl-4,4'-disulphonyl chloride, hexane-1,6-disulphonyl chloride, cyclohexane-I, 4-disulphonyl chloride, ethane-1,2-disulphony1 chloride, toluene disulphonyl chloride, p,p'-oxybis (benzenesulphonyl chloride), and compounds of the type XSO (CH ),,SO X

wherein X is F, Cl, Br, or I and n has a value from 2 to 12.

COMPONENT B.--(FIXATIVE) CONTAINING OCOX GROUPS Typically, one may employ compounds of the aliphatic, aromatic, or heterocyclic series containing at least two haloformatc (-OCOX) groups. The compounds may be subs tittued if desired with non-interfering (non-functional) substituents such as sulphone groups, ether groups, thioether groups, etc. Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: Ethylene glycol bischloroformatc, diethylene glycol bischloroformate, 2,2-dimethyl propane 1,3-diol bischloroformate, propane-1,3-diol bischloroformate, butane-1,4-diol bischloroformate, hexane-1,6-diol bischloroformate, octane-1,8-diol bischloroformate, decane-1,10-diol bischloroformate, butane-1,2-diol bischloroformate, hexane-1,2-diol bischloroformate, Z-methoxyglycerol-l,3-dischloroformate, glycerol-1,2-bischloroformate, glycerol-1,3-bischloroformate, diglycerol bischloroformate, hexanetriol bischoloroformate, pentaerythritol bischloroformate, cyclohexane-1,4-diol dischloroformate, hydroquinone bischloroformate, resorcinol bischloroformate, catechol bischloroformate, bischloroformate of 2,2-bis(parahydroxyphenyl) propane, bischloroformate of 2,2-bis(parahydroxyphenyl) butane, bischloroformate of 4,4-dihydroxybenzophenone, bischloroformate of 1,2-bis(parahydroxyphenyl) ethane, naphthalene-1,5-diol bischloroformate, biphenyl-4,4'-diol bischloroformate, glycerol trichloroformate, pentaerythritol tetrachloroformate, and the like. If desired, mixtures of different bishaloformates may be used.

Among the preferred compounds are the aliphatic bischloroformates, for example, those of the type wherein n has a value from 2 to 12. Another preferred category of compounds are the bis-chloroformates derived from polyethylene glycols, e.g.,

(H) o Cl-C-OCHz-CHz-[O CHz-CHzh-O CHz-CHz-O i-o1 16 wherein n has a value from zero to 10. A useful category of aromatic bischloroformates are the bisphenol chloroformates, that is, compounds of the type wherein RCR represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms, R is hydrogen or a lower alkyl radical.

It is also evident that the sulphur analogues of thebischloroformates may be used and such are included w1thin the spirit of the invention. Thus, instead of using the compounds containing haloformate groups, one may use any of the compounds containing the sulphur analogues of these groups, for example, the compounds containing two or more groups of the formula Z II c wherein one Z is sulphur and the other is oxygen or wherein both Zs are sulphur. The symbol X in the above formula stands for a halogen.

COMPONENT B.-(FIXATIVE) CONTAINING NHCOX GROUPS Aromatic, aliphatic, or heterocyclic compounds containing at least two carbamyl halide (NHCOX) groups. The compounds may be hydrocarbon carbamyl halides or may contain non-interfering (non-functional) groups such as ether, thioether, sulphone, etc. groups. Typical compounds in this category are given below by way of illustration and not by way of limitation: Ethylene dicarbamyl chloride, trimethylene dicarbamyl chloride, tetramethylene dicarbamyl chloride, hexamethylene dicarbamyl chloride, octamethylene dicarbamyl chloride, Z-methylpropane-l,2-dicarbamyl chloride, 2,6-dimethyloctane-2, 7-dicarbamyl chloride, cyclohexane-l,4-dicarbamyl chloride, diethyl ether-2,2'-dicarbamyl chloride, diethyl thioether-2,2'-dicarbamyl chloride, piperazine dicarbamyl chloride, 0-, m-, and p-phenylene dicarbamyl chloride, xylene dicarbamyl chloride, and their sulphur analogues, i.e., the corresponding dithiocarbamyl chlorides. if desired, mixtures of different dior tri-carbamyl halides may be used. It is generally preferred to use compounds of the type XCONH(CH -NHCOX wherein X is F, Cl, Br, or I and n has a value of 2 to 12.

COMPONENT B.(FIXATIVE) CONTAINING NH OR NH GROUPS Component B in this category may be any of the aromatic, aliphatic, or heterocyclic compounds containing at least two amine (-NH or imine (NH groups. The compounds may be hydrocarbon amines or imines or may contain non-interfering (non-functional) groups such as ether groups, thioether groups, sulphone groups, fluorine groups, etc. Typical compounds in this category are listed below by way of illustration but not limitation: Ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, N,N-dirnethy1-l, 3-propanediamine, 1,2-diamino-2-methylpropane, 2,7-diamino-2,6-dimethyloctane, N,N-dimethyl-1,6-hexanediamine, 1,4-diamino cyclohexane, 1,4-bis-(aminomethyl) cyclohexane, 2,2-diaminodiethyl ether, 2,2'-diaminodiethyl sulphide, bis-(4-aminocyclohexyl) methane, N,N'-dimethyl-2,2,3,3, 4,4-hexafluoropentane-l,S-diamine, ortho-, meta-, or paraphenylene diamine, benzidine, xylylene diamine, m-toluylene diamine, ortho-tolidine, piperazine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, 3,3- imino-bispropyl amine, 6,6'-imino-bishexyl amine, pentaerythritol amine, and the like. If desired, mixtures of the amines or imines may be used. It is generally preferred 17 to use aliphatic alpha, omega diamines, particularly of the type z 2)n z wherein n has a value of 2 to 12, preferably 6 to 10. Another preferred class is compounds of the type H N-(CH CH -NH) -H wherein n is 2, 3, or 4.

COMPONENT B (FIXATIVE) CONTAINING OH GROUPS Component B in this category may be any of the aromatic, aliphatic, or heterocyclic compounds containing at least two hydroxy groups. The compounds may be hydrocarbon polyols or may contain non-interfering (nonfunctional) radicals such as ether groups, thioether groups, sulphone groups, etc. Typical compounds in this category are listed below by way of illustration but not limitation: Ethylene glycol, diethylene glycol, 2,2-dimethyl propane-l,3-diol, propane-1,3-diol, butane-1,4- diol, hexane 1,6 diol, octane 1,8-diol, decane-1,10- diol, dodecane 1,12-diol, butane-1,2-diol, hexane-1,2- diol, l-O-methyl glycerol, 2-O-methyl glycerol, cyclohexane l,4-diol, hydroquinone, resorcinol, catechol, bis (parahydroxyphenyl) methane, 1,2 bis(parahydroxyphenyl) ethane, 2,2 bis(parahydroxyphenyl) propane, 2,2 bis(parahydroxyphenyl) butane, 4,4 dihydroxybenzophenone, naphthalene 1,5 diol, diphenyl 4,4- diol, 2,2 bis(3 methyl-4-hydroxyphenyl) propane, 2,2- bis(3 isopropyl-4hydroxyphenyl) propane, 2,2-bis(4- hydroxy-dibromophenyl) propane, glycerol, diglycerol, hexanetriol, pentaerythritol, etc. Moreover, it is within the spirit of the invention to utilize the sulphur analogues of the diols. Thus, for example, instead of using the compounds containing two hydroxy groups one can use the analogues containing either (a) two SH groups or (b) one SH group and one --OH group.

Among the preferred compounds are the aliphatic diols, for example, those of the type wherein n has a value from 2 to 12. Another preferred category of aliphatic compounds are the polyethylene glycols, i.e. I

wherein n has a value from zero to 10. A preferred category of aromatic diols are the bisphenols, that is, compounds of the type R HO( J OH it it 1'! wherein RC-R represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms, and R represents hydrogen or a lower alkyl radical. In this category especially preferred compounds are 2,2 bis(parahydroxyphenyl) propane, often designated as bisphenol-A; 2,2- bis(3 methyl 4 hydroxyphenyl) propane; 2,2-bis(3- isopropyl-4-hydroxyphenyl) propane; and brominated derivatives of bisphenol-A, such as 2,2-bis(4-hydroxy-dibromophenyl) propane.

The hydroxy compounds are employed as such in the phase boundry-limited cross-linking or in the form of their alkali-metal salts, that is, as alcoholates or phenolates, depending on whether the polyols are aliphatic or aromatic.

COMPONENT B (FlXATIVE) CONTAINING NCO GROUPS Component B in this category may be any of the aliphatic, aromatic, or heterocyclic compounds containing at least two isocyanate (NCO) groups. The compounds may be hydrocarbon isocyanates or may contain non-interfering (non-functional) radicals such as ether groups, thioether groups, sulphone groups, tertiary amine groups, etc. Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: Ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, cyclohexylene diisocyanate, bis(2 isocyanatoethyl) ether, bis(2 isocyanatoethyl) ether of ethylene glycol, o-phenylene diisocyanate, m-phenylene diisocyanate, pphenylene diisocyanate, tolylene 2,4-diisocyanate, tolylene 2,6 diisocyanate, 3,3 bitolylene 4,4-diisocyanate, diphenyl ether-4,4-diisocyanate, 3,5,3'5'-bixylylene- 4,4 diisocyanate, diphenylmethane 4,4 diisocyanate, biphenylene diisocyanate, 3,3 dimethoxy biphenylene- 4,4' diisocyanate, naphthalene diisocyanates, polymethyl polyphenyl isocyanates, and reaction products of polyhydric alcohols with excess diisocyanate, for example, compounds of the formulae (ilHz-Z wherein Z stands for the radical It is also evident that the sulphur analogues of these compounds may be used and such are included within the spirit of the invention. Thus, for example, instead of using the compounds containing two --NCO groups one may use their analogues containing either two NCS groups or one NCO group and one NCS group.

Among the preferred compounds are the aliphatic diisocyanates, for example, those of the type OCN(CH -NCO wherein n has a value from 2 to 12. Other preferred compounds are the toluene diisocyanates, xylylene diisocyanates, and diphenylmethane 4,4 diisocyanate which may also be termed methylene-bis(p-phenylisocyanate).

COMPONENT B (FIXATIVE) CONTAINING ANHYDRIDE OR IMIDE GROUPS Component B in this category may be any of the aliphatic, aromatic, or heterocyclic compounds containing at least two anhydride or imide groups. The compounds may be hydrocarbon anhydrides or imides or may contain non-interfering (non-functional) radicals such as ether groups, thioether groups, sulphone groups, tertiary amine groups, etc. Typical illustrative examples in this category are: 3,3',4,4'-benzophenone tetracarboxylic dianhydride or diimide, cyclopentanetetracarboxylic dianhydride or diimide, cyclohexanetetracarboxylic dianhydride or diimide, pyromellitic dianhydride or diimide, etc.

PROCEDURE As mentioned above, a feature of the present invention is that cross-linking of the pre-formed polymer takes place under phase boundary-limited reaction conditions. This means that Component A and Component B must be present on the fibrous substrate in separate phases so that the cross-linking reaction will take place at the boundary between the phases. This is, of course, a very desirable situation as under such conditions the cross-linking takes place almost instantaneously so that no after-treatment (curing) is required. The boundary may be between different types of phases-solid, liquid, or gaseouswith the proviso that at least one phase must be fluid, i.e., liquid or gaseous. Thus, the Component A may be present as a solid phase (e.g., applied in solution, followed by evaporation of solvent) and Component B as a liquid or gas phase. Where Component -A is applied as a liquid phase, Component B is applied as a solid, liquid, or gas phase. Generally, a system of liquid-liquid phases is preferred, and particularly wherein the phases are mutuallyinsoluble whereby to preserve the boundary between the phases. Thus, in a preferred embodiment of the invention, the selected Components A and B are formed into separate solutions, using solvents which are substantially mutually immiscible. Thus, for example, Component B is dissolved in water and Component A is dissolved in benzene, carbon tetrachloride, toluene, xylene, ethylene dichloride, chloroform, hexane, octane, petroleum ether or other petroleum distillate, or any other inert, waterimmiscible solvent. The two solutions are then applied to the fibrous substrate serially; that is, the substrate is treated first with one solution, then with the other. The order of applying the solutions is not critical. Generally, the solution of Component B is applied first and the solution of Component A is applied next. However, the reverse order gives good results and it is within the ambit of the invention to apply the solutions in either sequence.

The solutions may be applied to the fibrous material in any way as long as they are applied serially. A preferred method involves immersing the material in one solution, removing excess liquid as by the use of squeeze rolls, immersing the material in the second solution, and again removing excess liquid. To remove unreacted materials, solvents, etc., the material may then be washed and/or rinsed. Then, after drying, it is ready for use or sale. Conventional apparatus consisting of tanks, padding rolls, squeeze rolls, and the like are generally used in applying the respective solutions. The amount of each component applied to the fibrous material may be varied by altering the residence time in the solutions, the pressure exerted by the squeeze rolls, and by varying the concentration of the active ingredients in the respective solutions. To decrease carry-over of the solvent from the first treating solution to the second solution, the fibrous substrate after its immersion in the first solution may be subjected to drying conditions such as exposure to a current of warm air to evaporate at least part of the solvent and hence concentrate the solution carried by the fibers.

As noted above, a critical factor in the preferred form of the invention is that the complementary agents-Component A and Component Bare serially applied to the textile dispersed in solvents which are substantially mutually immiscible. The nature of the solvents is of no consequence as long as they are essentially inert and possess the above-stated property of substantial immiscibility. Usually, volatile solvents are preferred as they may be removed from the treated textile by evaporation. However, non-volatile solvents can be used, in which case they may be removed from the product by extraction with suitable volatile solvents therefor or washed out with soap and water or detergent and water formulations. In some cases Component A is soluble in Water and may thus be applied to the textile in aqueous solution. In such case the solvent for Component B may be any inert, essentially water-immiscible organic solvent. Typical illustrative examples thereof are benzene, toluene, xylene, carbon tetrachloride, ethylene dichloride, chloroform, hexane, octane, petroleum ether or other volatile petroleum fraction. Usually, however, Component A, because of its high molecular weight, is insoluble in water and is preferably applied in solution in a substantially water-immiscible organic solvent, such as any of those listed above. In such case, Component B would be applied in aqueous solution. It is, of course, obvious that many of the contemplated highly reactive groups will react with water (e.g., isocyanate, carbonyl halide, sulphonyl halide, carbamyl halide, haloformate, anhydride, and imide groups) and hence components which contain these are not normally applied in aqueous solutions.

Although one of the complementary solutions generally has water as a solvent, such a system is not essential and one may utilize a system of two essentially immiscible organic solvents, Component A being dispersed in one solvent and Component B in the other. As an example, Component A may be dispersed in 2-bromoethyl acetate and Component B dispersed in benzene. Another example involves using formamide, dimethylformamide, or diethylformamide as the solvent for Component A and using n-hexyl ether as the solvent for Component B. A further example involves a system of adiponitrile as the solvent for Component A and ethyl ether as the solvent for Component B. Examples of other pairs of solvents which are substantially immiscible with one another and which may be used for preparing the solutions of the respective reactants are Z-bromoethyl acetate and n-hexyl ether, ethylene glycol diacetate and n-hexyl ether, adiponitrile and n-butyl ether, adiponitrile and carbon tetrachloride, benzonitrile and formamide, n-butyl ether and formamide, di-N-propyl aniline and formamide, isoamyl sulphide and formamide, benzene and formamide, butyl acetate and formamide, benzene and nitromethane, n-butyl ether and nitromethane, carbon tetrachloride and formamide, dimethyl aniline and formamide, ethyl benzoate and formamide.

The concentration of active materials (Component A and Component B) in the respective solutions is not critical and may be varied widely. Generally, it is preferred that each of the pair of solutions contains about from 0.5 to 20% of the respective active component. In applying the process of the invention, enough of the respectiVe solutions are applied to the fibrous substrate to provide a cross-linked polymer on the fibers in the amount desired. In treating some substrates such as textiles it is desired to limit the amount of cross-linked polymer to about 1 to 10% of the weight of the textile, whereby to achieve the desired modification-cg. shrinkproofingwithout damaging the hand of the textile.

It is often desirable to add reaction promoters or catalysts to either of the solutions of Components A or B in order to enhance reaction between the active agents. For example, in cases where the system involves reaction between (1) amine or hydroxy groups and (2) carbonyl chloride, sulphonyl chloride, carbamyl chloride, or chloroformate groups, it is desirable to add to the solution of the component containing the amine or hydroxy groups a sufficient amount of alkaline material to take up the HCl formed in the reaction. For such purpose one may use a tertiary amine such as pyridine, dimethyl aniline, or 'quinoline or an alkali-metal hydroxide, or, more preferably, an alkaline material with buffering capacity such as sodium carbonate, sodium bicarbonate, trisodium phosphate, borax, sodium metasilicate, etc. Another plan which may be used in instances where one component contains amino groups, involves supplying said component in excess so that it will act both as a reagent and as an HCl-acceptor. The reaction of Components A and B may also be catalyzed by addition of such agents as tributyl tin chloride, stannous tartrate, ferric chloride, titanium tetrachloride, boron trifluoride-diethyl ether complex, or tin salts of fat acids such as tin laurate, myristate, etc. Such catalysts are particularly useful to promote reaction between components containing hydroxy groups and those containing isocyanate, acid chloride, or chloroformate groups.

Where one of the solutions of the reactants contains Water as the solvent, it is often desirable to incorporate a minor proportion of a surface-active agent to aid in dispersing the reactant and to assist in penetration of the solution into the textile. For this purpose one may use such agents as sodium alkyl (C8C13) sulphates, the sodium alkane (C -C sulphonates, the sodium alkyl c o benzene sulphonates, esters of sulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps, typically sodium salts of fat acids. Emulsifying agents of the non-ionic type are suitable, for example, the reaction products of ethylene oxide with fatty acids, with polyhydric alcohols, with partial esters of fatty acids and polyhydric alcohols or with alkyl phenols, etc. Typical of such agents are a polyoxyethylene stearate containing about 20 oxyethylene groups per mole, a polyoxyethylene ether of sorbitan monolaurate containing about 16 oxyethylene groups per mole, a disterate of polyoxyethylene ether of sorbitol containing about 40 oxyethylene groups per mole, iso-octyl phenyl ether of polyethylene glycol, etc. Generally, only a small proportion of surface-active agent is used, on the order of 0.05 to 0.5%, based on the weight of the solution. In addition to, or in place of the surface-active agent, a supplementary solvent may be added to the primary solvent (water) in quantity sufiicient to disperse the active reactant. For such purpose one may employ acetone, or other inert, volatile solvent, particularly one that is at least partially miscible with water. It is evident that the solutions of Components A and B need not necessarily be true solutions; they may be colloidal solutions, emulsions, or suspensions, all these being considered as solutions for the purposes of the present invention.

Ordinarily, the treatment of the fibrous substrate with the solutions of the complementary agents is carried out at room temperature as at such temperature the crosslinking takes place very rapidly, that is, in a matter of a minute or less. If, however, a higher rate of cross-linking is desiredas in continuous operation on long lengths of cloththe second solution may be kept hot, for example, at a temperature of 50 to 150 C. Also, where the agents used include a polyol as such (in contrast to the alkali salt thereof) it is preferable to heat the second solution as the cross-linking rates with the polyols are generally unsatisfactory at room temperature.

As has been explained above, in the preferred modification of the invention the solutions of Components A and B are serially applied to the fibrous material in the form of mutually-immiscible solutions to provide a liquid-liquid interface between the solutions as they are serially laid onto the fibers. In a less preferred modification of the invention, a system is used which utilizes a solid-liquid interface. Such a system is established in the following way: The fibrous material is first impregnated with a solution of one of the complementary agentsfor example, Component A-dispersed in an inert, volatile solvent. The substrate is then subjected to drying as by exposing it to a current of hot air. The fibers which are now covered with a deposit of the first component in a solid state, are then impregnated with the complementary agent-Component B, in this case, dispersed in an inert, preferably volatile solvent. In this way the fibers are layered with a superposed system of solid Component A and a solution of Component B. Under these conditions cross-linking takes place rapidly, forming the three-dimensional polymer in situ on the fibers. In this system it is not essential that the respective solvents be immiscible. Thus, for example, Component A may be applied in water solution and Component B in awater-miscible solvent such as dioxane or acetone. This and other phases not involving liquid-liquid boundary cross-linking are described in some of the examples below, e.g. Example I, runs 2 and 4.

In a preferred embodiment, the invention is applied to wool as the fibrous substrate whereby to attain such desirable results as increasing the resistance of the textile to shrinking and felting when subjected to washing operations, increasing the resistance of the textile to becoming soiled in use, enhancing resistance to bleaches and to light, decreasing the tendency of the textile to becoming creased or wrinkled during wear or during washing and drying operations, i.e., to provide it with easy-care properties so that ironing after laundering is largely eliminated. Moreover, these desirable effects are attained without impairing such desirable properties as tensile strength, abrasion resistance, elasticity, porosity, and hand of the material so that textiles modified in accordance with the invention may be used in fabricating garments of all kinds. The invention may be applied to wool in any physical form, for example, bulk fibers, top, sliver, roving, webbing, yarn, felt, woven textiles, knitted textiles, completed garments or garment parts, and other fabricated forms such as carpets, rugs, blankets, cords, tapes, etc. As noted hereinabove, the permanence of modification obtained in accordance with the invention is primarily based on converting the pre-formed polymer into an insoluble, crosslinked (B-dimensional) structure. However, it is evident that in treating wool in accordance with the invention, one may additionally obtain a chemical combination of the polymer with the wool in such cases where the pre-formed polymer and/or the fixative contains groups capable of reacting with reactive sites on the wool molecules. Since such reactive sites are primarily of an amine or hydroxy nature, it is believed that chemical combination (grafting) occurs in such instances where the agents applied (Components A or B) contain such reactive groups as carbonyl halide, haloformate, sulphonyl halide, carbamyl halide, isocyanate, etc.

Although the invention is of particular advantage in its application to wool, this is by no means the only type of fiber which comes into the ambit of the invention. Generically, the invention is applicable to the treatment of any type of fibrous material, for example, animal hides and leather; silk, animal hair, mohair; cotton; sisal; hemp; jute; ramie; flax; wood; paper; synthetic cellulosic fibers such as viscose, cellulose acetate, cellulose acetate-butyrate, saponified cellulose acetate, cupra-ammonium rayons, ethyl cellulose; polyvinyl alcohol-protein fibers; algin and pectin fibers; glass fibers; asbestos; organic non-cellulosic fibers such as polyethylene terephthalate, polyacrylonitrile, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, nylon, polyurethanes; regenerated protein fibers such as those prepared from casein, soybeans, peanut protein, zein, gluten, egg albumin, collagen, or keratins such as animal hoof or horn; mixtures of any of the above such as textiles containing cellulosic and non-cellulosic fibers, blends of synthetic fibers or cotton with wool, etc. The invention may be applied to such fibrous materials in any state such as bulk fibers, staple fibers, slivers, yarns, woven or knitted textiles, felts, fabricated articles such as gannents and garment parts. The application of the invention may be for the purpose of obtaining any of a wide variety of functional or decorative effects such as sizing, increasing gloss or transparency, increasing water-, oil-, or soil-repellency, increasing adhesion or bonding characteristics of the substrates with rubber or other elastomers, imparting softness or lubricity, imparting shrinkage resistance, decreasing tendency to wrinkle, crease and pill during wear or during washing and drying operations, etc. In cases where the fibrous material is a hydrogen-donor (that is, where its molecules contain active hydrogen as in amine or hydroxy groups), it would be expected that during application of the process of the invention, a chemical combination of the polymer to the fiber molecules will take place, particularly where either the preformed polymer or the fixative contains such highly reactive groups as carbonyl halide, sulphonyl halide, carbamyl halide, haloformate, or isocyanate. Typical examples of hydrogen donor fibers (in addition to wool) are the natural cellulosic fibers, viscose rayons, saponified cellulose acetate fibers, etc.

Having now described the types of compounds which may be used as Components A and B and how they are applied to fibrous materials, we will next explain the various preferred embodiments of the invention. In the procedure of the invention, the type of pre-formed polymer employed is the determinative factor because of the large molecular weight thereof in comparison to that of the fixative or the cross-linking units derived therefrom. Accordingly, the various sub-generic embodiments of the invention are based on the type of pre-forrned polymer, i.e., Component A.

EMBODIMENT 1 In this preferred embodiment of the invention, Component A is an addition polymer. Numerous examples thereof are listed hereinabove in the sections entitled Component A (Addition Polymers) and Component A (Converted Addition Polymers). Among the special advantages of addition polymers for use as Component A are stability to oxidation and light, good film-forming ability, availability of a Wide spectrum of types and individual species, and the fact that many are relatively inexpensive compared to other classes of polymers.

In the preferred practice in accordance with this embodiment of the invention, Component A is an addition polymer containing (as the highly reactive groups) carbonyl halide, sulphonyl halide, haloformate, isocyanate, carbamyl halide, or anhydride groups and is applied to the fibrous substrate in the form of a solution in an inert, essentially water-immiscible solvent. The complementary fixative (Component B) is accordingly applied as an aqueous solution and contains hydroxy groups, or, more preferably, amine or irnine groups as the highly reactive groups complementary to those on Component A. Thus in operating in the sphere of the preferred modification of this embodiment, Component B may be chosen from any of the types exemplified above in the section entitled Component B (Fixative) Containing NH or NH Groups.

Coming under special consideration is the use, as Component A, of copolymers of (a) methacryloyl chloride or acryloyl chloride (to provide free COCl groups) with (b) other polymerizable unsaturated monomers free from highly reactive groups, typically such monomers as olefines, esters of acrylic or methacrylic acid, vinyl esters and ethers, vinyl chloride, etc.

Especially useful are the copolymers containing units derived from (1) acryloyl or methacryloyl chloride and (2) from an olefine such as ethylene, propylene, isobutylene, or butadiene. Usually, a third type of unit is included to decrease crystallinity and to increase solubility. For these purposes, the copolymer may contain units derived from (3) esters of acrylic or methacrylic acid, vinyl esters of fatty acids, vinyl ethers, vinyl chloride, or the like. These copolymers may be directly prepared from the monomers. More usually, acrylic or methacrylic acid is copolymerized with the olefine and the third type of monomer and the product is treated to convert the free acid groups to carbonyl chloride groups. Thus although not made directly, the final product can still be considered as a copolymer of acryloyl or methacryloyl chloride with the olefine and the third type of monomer. A typical formulation for this type of copolymer would be, for example, 1 to 10 mole percent of methacryloyl chloride, 5 to mole percent of vinyl acetate, or the like, and the remainder (to 100 mole percent) of the olefine.

This Embodiment 1 of the invention is further demonstrated by the following illustrative examples:

EXAMPLES Accelerotor shrinkage test.This test for shrinkage was conducted in the following way: The wool samples were milled at 1700 rpm. for 2 minutes at 4042 C. in an Accelerotor with 0.5% sodium oleate solution, using a liquor-to-wool ratio of 50 to 1. After this washing operation the samples were measured to determine their area and the shrinkage was calculated from the original area. The Accelerotor is described in the American Dyestuff Reporter, vol. 45, p. 685, Sept. 10, 1956. The two-minute wash in this device is equal to about home launderings. Washing machine shrinkage test.The wool samples were washed in a reversing agitator-type household wash- 5 ing machine, using a 3-lb. load, a water temperature of 105 F., and a low-sudsing detergent in a concentration of 0.1% in the wash liquor. The Wash cycle itself was for 75 minutes, followed by the usual rinses and spin drying. In most cases this washing program was repeated several times. The damp material was then tumble-dried in a household-type clothes dryer. The samples were then measured to determine their length and width and the shrinkage calculated from the original dimensions.

Oil repellency test.The 3M oil repellency test described by Grajeck and Petersen, Textile Research Journal, 32, pp. 320-331, 1962. Ratings are from 0 to 150, with the higher values signifying the greater resistance to oil penetration.

Water repellency.-AATC spray test, method 22-1952. Ratings are from 0 to 100 with the higher values signifyin g greater resistance to water penetration.

Example I (1) Solution A: Component A was a terpolymer of ethylene (80%), vinyl acetate (15%), and methacryloyl chloride (5%). Its molecular weight was about 50,000 and it contained about 40-50 carbonyl chloride groups per polymer molecule. Solutions were made of this terpolymer in methyl chloroform at concentrations of 3% and 1.5%.

(2) Solution B: 0.5 percent hexamethylene diamine (Component B), 1% sodium carbonate, and 0.05% wetting agent (isooctylphenyl ether of polyethylene glycol) in water.

(3) A sample of wool cloth was immersed in one s0lu tion at room temperature for about 30 seconds, run through squeeze rolls to remove excess liquid, immersed for about 30 seconds in the complementary solution at room temperature, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air at room temperature.

(4) The sequence of treatment with the respective solutions and the results of shrinkage tests on the products are tabulated below:

Cone. of terpolym er Area shrinkage in Sol. A, (Accelerotor),

percent percent Order of applying solutions Run U! in 5. A Control (Untreated wool) 1 In these cases, the cloth, after application of solution B, was air dried prior to immersion in solution A.

Example II Percent Area shrinkage, Order of Cone. of cumulative 1 Run applying terpolymer solutions in Sol. A, l ash Wash Wash Wash percent 1 2 3 4 3 0. 2 0. 5 0. 3 0. 5 l 0. 2 0. 9 0. 4 l. 0 0. 5 l. 0 3. 5 4. 7 9. 4 3 0. 3 1. 5 0. 5 0. 5 Control 19. 1 30. 5 35. 5 39. 5

25 The products of runs 1, 2, and 3 were subjected to tests for abrasion resistance, using a Stoll flex abrader, ASTM:D1175-5ST. The results are as follows:

Wt. resin Abrasive resistance, Run on fabric, cycles to break percent Warp Fill 1 3 810 767 1 716 969 3 0. 5 550 588 Control (Untreated) 457 547 The products of runs 1, 2, and 3 were tested for their coefficient of friction by drawing individual fibers over a glass rod in the direction against the scales. In this test a smaller value indicates a smoother fiber surface. The results are given below:

Wt. resin Friction coefiicieut Run on fabric, (against scales) percent 3 152 1 174 3 0. 214 Control (Untreated) 0 230 Example III listed below:

Diamine: Abbreviation Ethylene diamine EDA 1,3-diaminopropane DPA Propylene diamine PDA Hexamet-hylene diamine HMDA Piperazine Pip Wool cloth was treated with the solutions as in Example I, part 3. In all cases the sequence of treatment was B-A. The results are given below:

Component B Percent area shrinkage, cumulative 1 Run used Wash 1 Wash 2 Wash 3 Wash 4 l Successive 75-minute washes in automatic home washing machine, as described above.

Example IV Solution A: The same terpolymer as in Example I was dissolved in methyl chloroform (or Stoddard solvent) at a concentration of 1.5

Solution B: Same as in Example III.

Wool cloth was treated with the solutions as in Example I, part 3. In all cases, the sequence of treatment was B-A. The results are given below:

26 Example V A solution of 95 ml. styrene, 5 ml. methacryloyl chloride, and 1000 ml. of benzene, containing 0.2 g. azo-bisisobutyronit-rile, was swept with dry nitrogen for 30 minutes and then heated to -80 in a closed vessel for 8 hours. The resulting solution of the styrene-methacryloyl chloride copolymer (containing more than 3 carbonyl chloride groups per molecule) was used to treat test swatches of wool as in Example I, part 3. Various aqueous solutions of diamines were used in the first treatment step; these diamine solutions contained 0.5% of the specified diamine, 1.0% sodium carbonate, and 0.1%

etting agent. Abbreviations for diamines are given in Example III.

Percent Area Shrinkage, Accelerotor Step 1 (Diamine used) Step 2 EDA- HMDA" Example VI A copolymer of methyl methacrylate and methacryloyl chloride (containing over 3 carbonyl chloride groups per copolymer molecule) was prepared as follows: 95 ml. of methyl methacrylate (redistd) and 5 ml. of methacryloyl chloride were placed in 500 ml. of dry benzene. The system was flushed with dry nitrogen, 0.1 g. azo-bis-isobutyronitrile added, and heated at 70-80 degrees C. for 6 hours while held in a closed vessel.

The resulting copolymer solution was used to treat test swatches of wool (14 inch by 14 inch): The test piece was first immersed in a solution, at room temperature, of 0.5% ethylene diamine in H O (containing 1.0% sodium carbonate and 0.1% wetting agent), then passed through squeeze rolls to give a wet pickup of about 60%. The swatch was then immersed in the copolymer solution, at room temperature, and again passed through the squeeze rolls, followed by a light 15-minute wash in 0.1% detergent solution, and finally dried at room temperature. The treated material shrank only 12% in a -minute wash in home washing machine, compared to 22% shrinkage by an untreated swatch.

Example VII A copolymer of lauryl methacrylate and methacryloyl chloride (in 95/5 mole ratio) was prepared by a standard bulk polymerization technique-Le, heating in a closed vessel at for 5 hours in the presence of a minor proportion of u,a-azodiisobutyronitrile as a polymerization initiator. The copolymer contained three or more carbonyl chloride groups per molecule.

Solution A: The copolymer above was dissolved in toluene at a concentration of 5% and 2.5%.

Solution B: Four percent ethylene diamine, 7% sodium carbonate, and 0.01% wetting agent (isooctylphenyl ether of polyethylene glycol) in water.

Wool cloth was treated with the above solutions as in Example 1, part 3, applying the solutions in the order B-A. In a control run, impregnation in Solution B was omitted.

Solvent for Component 13 Percent area shrinkage, cumulative 1 Run Component A used Wash 1 Wash 2 Wash 3 W'ash 4 1 Methyl ehloroior1n EDA 1.3 2.0 3.0 1. 3 2 do DPA 0. 7 2. 5 3. 2 3. 5 '1 d0, PDA 1.0 1.9 2.5 2.2 4 do HMDA 0.2 0.5 0.2 0 5 do Pip." 1.2 1.5 2. 7 2.2 6 Stoddard solvent. EDA 0 0 0 0.7 do.. HMDA 0.8 0.6 0.3 0.7 Control 18. 8 30. 5 36. 4 39. 5

1 Successive 75-minute washes in automatic home washing machine, as described above- The products were tested for shrinkage and also for Example X permanence of the copolymer deposit by extraction with I The chloroformate of ethylene glycol rnethacrylate benzene for 2 /2 hours 1n a Soxhlet extractor. The results CH O are tabulated below:

CHz=C-C-OCH2-CHz0CCl Weight of polymer on Percent Area Cone. of fabric, percent shrinkage, Procedure copolymer cumulative 1 in Sol. A,

percent Before After Wash 1 Wash 2 extraction extraction 5 2. 2 1. 5 1 0 l 3.0 2.5 1.5 N.d. 3.4 9.0 5 5.2 0.2 7.0 13.0 10.0 20.0

1 Successive 75-minute washes in automatic home washing machine, as described above. 2 Shrinkage tested after extraction.

3 Shirnkage tested before extraction.

N.d.==Not determined.

Example VIII was prepared in 95% overall yield by reaction of ethylene glycol monomethacrylate with excess phosgene. The chloroformate was purified by distillation, B.P. 85 C. at 3 mm.

The chloroformate was copolymerized with lauryl rnethacrylate to produce a copolymer containing at least 3 chloroformate groups per molecule, using the following Treatment of wool with a terpolymer containing sty- 2O rene, lauryl rnethacrylate and methacryloyl chloride, the terpolymer containing three or more carbonyl chloride groups per molecule.

The terpolymer was prepared, using the following recipe: technique. Styrene ml 52 Lauryl rnethacrylate (15 g.), 5 g. of the chloroformate, Lauryl rnethacrylate ml 100 ml. dry benzene, and 200 mg. a,e-azodiisobutyro- Methacryloyl chloride ml 10 nitrile were heated in a closed vessel at 79 C. for 18 Benzene ml 900 30 hours. Azo-bis-isobutyronitrile g 0.2 Solution A: The copolymer solution prepared as given above.

The system was swept free of air by sweeping with dry nitrogen and was kept under a nitrogen atmosphere during 10 hours of heating in a closed vessel at 70-80 C. The resulting terpolymer solution was used to treat wool swatches: The test swatches were first dipped in a 0.5% aqueous solution of a diamine, passed through a squeeze roll, then immersed in the terpolymer solution, again passed through the squeeze roll, and finally given a light wash in 0.1% detergent solution and dried at room temperature. The following results were obtained when the swatches were washed in an accelerated shrinkage test,

Solution B: Three percent hexamethylene diamine and 0.01% wetting agent (isooctylphenyl ether of polyethylene glycol) in water.

W001 cloth was treated with the above solutions as in Example I, part 3, applying the solutions in the order BA. In a control run, impregnation with solution B was omitted.

The products were tested for shrinkage before and after an extraction with chloroform20 hours in a Soxhlet extractor. The results are given below:

Perce tA ea usmg the Accelerator P d Approxkvtghoi shrinkagm Acc lerotor I'OCG ure leSlIl 011 3. no, Step 1 step 2 Area zl g g percent Before After D extraction extraction HMDA Terpolymer 501m" 6 In accordance with invention 15 2 5 EDA d 5. 0

Control (Untlmtcd) Blank (N 0 treatment) 30 Example IX E 1 XI xam e 1,1-d1hydroperfluorooctyl acrylate (9 moles), methap cryloyl chloride (1 mole), and or,a'-azodiisobuyronitrile solutlqfl A: Component was P Y (about 5 as a polymerization initiator were heated methyl vinyl ether and maleic anhydrrde having a specific gether at 78 C. for 3 to 4 hours in a closed vessel. The 5 Vlscoslty of t0 1% s lution in methyl-ethyl resulting copolymer containing three or more pendant ketone at 25 The repeatmg mm of this copolymer COC1 groups per molecule was a tacky, solid resin. had the structure Solution A: The above polymer was dissolved in 1,3- OCH: bis(trifluorornethyl) benzene at a concentration of 3%. OHZ CII CIICH Solution B: Two percent hexamethylene diamine, 2% sodium carbonate, and 0.01% wetting agent (isooctylphenyl ether of polyethylene glycol) in water. 0

1 610th Was treated Wlth these 5011150115 in It was dissolved in ethyl acetate at concentrations of 3,

ample I, part 3, applying the solutions in the order BA. 1,5, d (17%, In a control run, impregnation in Solution B WaS omitted. 65 Solution B; Two percent hexamethylene diamine, 3%

Increase in weight in both cases was 1%. The products odium arbonate, and 0.01% Wetting agent (isooctylwere tested for or1 and water repellency as prepared and phenyl ether of polyethylene glycol) in Water. after extraction with benzotrifiuoride for 6 hours in a Wo l loth wa t t d ith th above s luti a in Soxhlet extractor. The results are given below: Example I, part 3, using the sequence BA.

Oil repellency Water repellency Procedure Before After Before After extraction extraction extraction extraction In accordance with invention 110 110 90 Control (No treatment with Sol. 13) 120 0 50-00 Blank (Untreated) 0 0 50-60 50-60 29 30 Tests for permanency of the finish were conducted by Example XIV measuring loss in weight after extraction for 6 hours with acetone. The product retained 95% of the resin deposit g gg of methacryloxymethyl pentamethyldl in this test. In a control test wherein treatment with Solution B (the fixative) was omitted, the cloth retained only 5 24% of the copolymer deposit. CHz-Si-OSiCH O-CO-CH In other runs, wool cloth was immersed in an acetone solution of the copolymer, squeezed to remove excess t liquid, air dried to evaporate the acetone, immersed in an and the chloroformate of monoethylene glycol methaqueous solution of 4% hexamethylene diamine, 7% 10 acrylate sodium carbonate, and 0.01% wetting agent (isooctyl- CH3 giigngihecithizrgiof polyethylene glycol), .then rinsed in water IL C0 C1 The product was extracted with acetone for 6 hours and it was found that the product retained 93% of the resin CH CH CH3 Was prepared by heating the following ingredients in a closed vessel at 75 C. for 10 hours:

deposit.

Example XII Siloxane compound as above grams 1.5

Solution A: Component A was chlorosulphonated polychloroformate fompound as above ethylene of number average molecular weight about Dry (dlluent? 30 000 and of the formula 0t,0s'-AZObISISObUtYIOIlltIllG (polymerization initiator) gram 0.1

l7 OH CH CH OBI-CH OH OH2-CH- 2- 2- I P 2- The VlSCOllS syrup resultmg was diluted with additional I 01 S0201 toluene to 3% and 6% concentrations and used as Soluwherein n is approximately 17 and x is approximately 12. tion A.

It was dissolved in benzene at a concentration of 1.5%. Solution B was a 5% solution of hexamethylene di- Solution B: 0.5 percent of hexamethylene diamine amine and about 0.01% non-ionic wetting agent in water. (HMDA) or ethylene diamine (EDA), 1% sodium car- Wool cloth was treated with the solutions as in Example bonate, 0.05% of wetting agent (isoootylphenyl ether of I, part 3, using the sequence B-A. The results of tests on polyethyleneglycol) in water. the products are given below:

Water repellency Area shrinkage (Accelcrotor, Wt. resin on fabric, percent Before After After after extraction extraction extraction 1 Accelerotor percent wash 6 80 100 100 ll. 6 3 80 100 100 16. 3 Control (Untreated) 50 27.0

1 Extraction was with benzene, 3 hours in a Soxhlet extractor.

Wool cloth was treated with these solutions as in Ex- EMBODIMENT 2 ample 1 part apPlymg lg ip f flji zggf In accordance with this embodiment of the invention, .(room l zf a l g i g m1 T b 1 Component A is a polyalkylene imine. Typical examples lmmerslon 6 re u s are glven e o of such polymers are exemplified above in the section entitled Component A (Polyalkylene Imines). A special Component]; Percent area shrinkage, cumulative, feature of these polymers 1s that they contaln built-1n Run used highly reactive groups on the polymer backbone, namely, Wash 1 Wash 2 Wash 3 Wash 4 NH- groups. In addition, they contain terminal NH 1 HMDA 0.3 1.9 3.7 5.0 groups. Another feature is that they are soluble in water f 3:? 3:2 2:; $512 even at very high molecular weights, e.g., 10,000 and x p I above. Accordingly, they may advantageously be applied as iggf ifgg g fiff Washes m automatlc home washmg mac me to the fibrous material in the form of an aqueous solution. The fixative (Component B) in such case is then prefera- Example XI bly applied as a solution in an inert, substantially waterimmiscible solvent. Component B is preferably chosen Wool cloth was immersed inasolut-ion containing 10% to provide isocyanate radicals as the complementary, ethylene diamine in a etone, The cloth was queezed to highly reactive groups. Other fixatives which provide excelremove excess liquid and air-dried to remove the solvent. lent results are those containing carbonyl halide, halo- It was then immersed in a 5% solution of the chloroformate, or anhydride groups. Thus the preferred types sulphonated polyethylene (as in Example XII) for 2 Of compounds for use as the fixative may be selected from minutes, squeezed and air-dried. those examplified above in the sections pertaining to Com- A piece of the treated cloth and a control (untreated) p0nent B of the types containing NCO, COX, OCOX, or piece were placed in 5% sodium hypochlorite solution in anhydride groups.

water and observed to ascertain dissolution time of each. s mb m nt 2 Of t e in ention is further demon- The results are given below: strated by the following illustrative examples:

Example XV 'f i z i sgfi Treated Component A was a polyethylene imine of molecular weight about 30,00040,000. Basically, this polymer had 10 Vigorous evolution of No evidence of attack. h structure bubbles. 20 Mostly dissolved Do. 120 Completely dissolved Still essentially whole;

attack at edges. L J

Solution A: Aqueous solution of the above polyethylene imine (concentration as given below) plus ca. 0.01% 9 resin Aral Shrinkage non ionic Wetting anent P c dure on fabric, percent (Accelcrotor), percent a 10 Solution B: Benzene solution containing 4% of toluene 39 59 r n gf g diisocyanate (TDI) or sebacoyl chloride (SC). e! m 1 ex Wool cloth was treated with the above solutions as deaccordance with invention 3. 4 l. 7 4. 0 6. 0 scribed in Example 1, part 3. Control (No applic The particulars of the treatment, amount of resin de- B 0 posited on the fabric, and shrinkage tests are given below:

Cone. of Percent Area Order of treatment Component A Component Wt. resin shrinkage, cumulative in B On Fabric Percent Percent Wash 1 Wash 3 Washfi 3 2.3 0 o 4 3.6 0 1.0 2.0 1 1.0 0 1.0 1.0 0.5 0.45 0 1.0 2.0 0.25 0. 22 o 1.0 1.5 3 2.9 0 1.0 2.0 3 2.3 o 1.0 2.0 2 1.4 0 1.0 3.0 10 9. 0 a. 0 13. 5 20. 0 None None 9. 0 26. 0 33. 4

Successive 75-minute washes in automatic home washing machine, agitator type, as described above.

Several of the products as prepared above were sub- EMBODIMENT 3 jected to extraction with acetone for 3 hours in a Soxhlet In accordance with this embodiment of the invention, extractor to test the permanence of the cross-linked resin Component A is a polyurethane, or, more accurately, a

deposits. AlSO, shrinkage tests were determined after SUCh polyether (o polyester) containing internal urethane extraction. The results are tabulated below: groups and free isocyanate groups. Typical examples of Gene. of Wt. of resin on Area shrinkage Component A Component fabric, Percent (Aecelcrotor, Order of treatment in Sol. A, B after extraction),

Percent Before After Percent extraction extraction 13-41-..- 3 2.3 1.7 0 A-B. 4 3. 6 3. 2 2. 0 A-B 3 2. 9 2. 3 2. 0 B-A. 3 2. 8 2. 2 2. 0 Control (A only)... 10 9. 0 2.6 10.0 7 Blank None do 27.0

Example XVI such polymers are exemplified above in the sections en- Solution A: Aqueous solution of the polyethylene imine gg? g g ff g f F ff 23 i g 22 2 described in Example XV (concentration given below) ye rs w cram 1 15 exp am a p y plus 0.01% nonionic Wetting agent mers may be prepared by reacting a polyether (or poly- Solution B: Acetone solution containing 4% pyromelfaster) contammg hydroxy groups wlth an excess of a m dianhydride 1socyanate. An advantageous feature of the polyurethanes Wool swatches were treated in the following manner: tllat when h are crosshnked in the Phase boundary The swatches were wet-out in Solution B, passed through 4r llmlted twn, they are converted into urethane a squeeze 1.011 to obtain about a 90% wet pickup, and 0 elas tomers and as a result the treated textile material air dried at room temperature for about 20 minutes to exhlb1t arllespeclany Soft and full P remove the acetone solvent. The dried swatches were then Ordmar} the polyul'ethane comam free f immersed in Solution A at room temperature for one anate radicals as thehighly reactive groups and since minute, passed through a squeeze roll to 90% wet pick-up. these are water'sFnsmve the polyfner 1S PR to the washed to remove unreacted materials, and air dried librous substrate 1n the form of an inert, essentially water- The various products were tested for permanence of immiscible solvent such as benzene, toluene, or the like. the resin deposit by extraction with acetone for 3 hours in Th6 fixative (comPonent B) 15 then Preferably PP a Soxhlet extractor. Shrinkage was also tested after exas an aqueous Solutlon- Component B Is Pmfgrably Chosen to provide amine or imine radicals as the complementary,

tr ct'o .The results are iven below.

a l n g highly reactive group. Typical examples are given above cor t z r A Wt. oiresiu outabric, perce in the section entitled Component B (Fixative) Coni rl Sol. A Before After extraction), 56mm taming NH 2 i NH p 9 7 In a variation of the basic procedure of this embodimerit, one may apply-as Component Aa polymer of 27.0 60 the class of polyethers (or polyesters) containing free hydroxy groups. Typical examples of these are given in Example XVII the above sections entitled Component A (Polyethers) Wool swatches were immersed in an aqueous solution and component A y In such Case 0116 would utilize as Component B a compound containing containing 3.3% of polyethylene imine (as described in free isocyanate groups (such as those exemplified above Example XV) and passed through squeeze rolls to a 100% wet pick-up. The swatches were air-dried at room Section entitles; Component B (FiXatiVe) C011- temperature. The cloth was placed in a cylinder wherein 11111118 NCO ps In uch case the end result of i was exposed to a current f nitrogen carrying vapors the phase boundary-limited reaction w1ll be a cross-linked polyurethane polymer.

of toluene diisocyanate. Following this treatment, the

ThlS Embodiment 3 of the inventlon 1s further illuswool was washed and air-dried.

This product and a control, in which the exposure to Hated below: toluene diisocyanate was omitted, were tested by extrac- Example XVIII.-Application of an Isocyanatetion with acetone for 3 hours in a Soxhlet extractor. Containing Polyurethane i0 W001 Shrinkage tests were also conducted before and after Poly(propylene oxide) glycol of an average molecular extraction. The results are tabulated below: weight 2000 and a hydroxyl number of 56 was chainextended and end-capped with 2,4-tolylenediisocyanate in the following manner: A dry, 3-neck, 500-ml. flask, fitted with stirrer, dropping funnel, nitrogen inlet and thermometer was charged with 100 g. (0.05 mole) poly (propylene oxide) glycol (average molecular weight 2000) and this was heated with stirring under nitrogen to 75 C. Tolylene diisocyanate (17.4 g.-0.l mole) Was then added slowly'over a 15-20 minute period via the dropping funnel. The mixture was stirred at 75-80 C. for 3 hours. An infrared spectra of the viscous syrup showed no free -OH but did show the expected strong band at 4.4 microns (N=C=O) and a weak band at 5.8 microns,

in Example I, part 3, using the sequence B-A. Shrinkage tests of the products are given below:

Percent Area shrinkage, cumulative l Diamme used 1 In successive 75-minute washes in automatic home washing machine, as described above.

Example XX Solution A: A polyoxypropylene triol (average molecular weight 1500; average hydroxyl No. 112) was dissolved 0 H in acetone at various concentrations as given below: Solution B: Three percent by volume of toluene diarising from chain coupling. The polymer was dissolved isocyanate in benzene. in dry toluene. Polymer concentrations of 9 and 2% Wool cloth was treated as described in Example I, part were used as Solution A. The aqueous treating Solution 3, using the sequence A-B and the cloth was air-dried B contained 4% (by volume) of triethylenetetramine and after removal from Solution A and prior to entering into ca. 0.01% of the wetting agent (isooctylphenyl ether of Solution B. polyethylene glycol). The products, and a control sample in which the treat- Wool cloth was treated with the solutions as in Exment with Solution B was omitted, were tested for shrinkample I, part 3, using the sequence B-A. As a control, age before and after extraction with acetone for 3 /2 hours in one run the treatment with Solution B was omitted. in a Soxhlet extractor. The results are given below:

Cone. of poly- Area shrinkage (Aeoxypropylene- Wt. of resin celerotor), percent Procedure triol in Sol. A, on fabric,

percent percent Before ex- After extraction traction In accordance with invention 4 4 4. 0 7.0 Do 2 2 5.9 N.d. 130..--

1 1 7.8 N.d Do 0.5 0.5 7.8 N.d Control (Treated with Sol. A only)- 4 4 18. 1 23. 4 Blank (Untreated) 27 N.d. -Not determined.

Tests were carried out to determine the shrinkage characteristics of the treated samples and also their permanence to extraction (with benzene, 3 hours). The results are tabulated below:

Wt. of resin on fabric, Area shrinkage Percent (Acelerotor), Percent Procedure Before After Before After extraction extraction extraction extraction In accordance with invention 3. 3

2. 3 o 1. 6 1 N .d N.d. Control (N o treatment with Sol. B) 8.0 0 8. 6 22.0 Blank 27 1 N.d.=Not determined.

It was observed that the products in accordance with the invention had a fuller, softer hand than the original (untreated) fabric.

Example XIX EMBODIMENT 4 In accordance with this embodiment of the invention, Component A is a polyamide. Typical examples of such polymers are given above in the section entitled Component A-Polyamides. Especially preferred are the polyamides containing free primary or secondary amino groups. A useful class of such polymers may be prepared, in known maner, by reacting an aliphatic polyamine such as one of the formula (wherein R is a short chain alkylene radical such as CH CH and n is 2 to 4) with heat-dimerized, unsaturated, high molecular weight fatty acids. The polyamides of this type are readily emulsifiable in water and may be applied to the fibrous substrate in such form. In this event, Component B is preferably applied in solution in an essentially water-immiscible, organic solvent such as benzene, toluene, or the like. Since the highly reactive groups of the preferred class of polyamides are primary or secondary amino groups, Component B is selected to contain complementary reactive groups, e.g., carbonyl halide, sulphonyl halide, haloformate, carbamyl halide, anhydride, or isocyanate. Suitable compounds of these types are given above in the sections listing the various types of Component B. Generally, compounds containing isocyanate groups are preferred as they not only form the cross-links rapidly but cause no evolution of acidic by-products (as is the case with acid halide fixatives).

Another useful plan for applying the aforesaid polyamides containing free amino groups involves applying the 35 36 polyamide to the substrate as a solution in a hydroxylatecl The products of Run 1 in accordance with the invention organic solvent such as ethanol or isopropanol (in which and the control (Run 9) were subjected to shrinkage tests they are easily soluble). The treated substrate is then before and after extraction with isopropanol for 5 hours dried to remove the solvent and the substrate then treated in a Soxhlet extraction. The results are given below:

wt. of resin on fabric Area shrinkage (Accelcrotor) percent Run Procedure Before After Before After extraction extraction extraction extraction 1 In accordance with invention.. 20 20 0 0 9 CoBn)trol (No treatment with Sol. 12 0 22 23. 3 1o- Blank (Untreated) 21 with the isocyanate-containing fixative dissolved in a sol- Example XXII vent such as benzene or toluene thus to accom lish the crossJinkiI-lg at a solid liquid b0u;1dary p 15 SOIUUIOII A! The polyamlde Of Example XXI was dis- This Embodiment 4 of the invention is further illussolved P 9 mmtrailPn of one Hated below. volume of this solution was poured into 5 volumes of water containing ca. 0.01% of non-ionic wetting agent, Example XXI applying vigorous agitation to form an emulsion. This Component A was a polyamide-a condensation prod- 20 emulsion was further diluted to various concentrations as uct of diethylene triamine and heat-dimerized unsaturated Elven f (mainly C fatty acidscontaining free primary and Soution B: Two percent toluene dnsocyanate in methyl secondary amine groups. An idealized structure of this chloroformcompound may be represented by the following:

I"? I? H;NCHr-CHr-NH-CH2-CH2-NIIT( ERCNHCHzOH2-NIICH:-OH;NHJ

wherein O ll R II Samples of wool cloth and wool top (wool top is a represents the acyl radical of the dimenzed fat acid and n thick but very open and loosely assembled strand of wool is the number of repeating units, usually about 20 to 60. fibers with no twist) were treated with the solutions as The P9 Y h an afmfle Value Of -320 (aml described in Example I, part 3, using the sequence A-B. value Is the milllgrams equivalent of KOH per gram of Tests for shrinkage of the products are tabulated below:

polyamide) and a viscosity in a Brookfield viscometer at C. of 80-120 poiscs.

Cone. of Area shrinkage Lengrhwise Procedure polyamide of fabric shrinkage of top in Sol. A, (Accelerator), (Accelerator),

Percent Percent In accordance with invention 6. 9 3. 4 Do 7.8 5.3 Do..- 10.7 3.2 Do 12.3 9.5 Control (Treated with Sol. B only) 27 15. 0 Control (Treated with Sol. A only) 27 18 Blank (Untreated) 27 25 Solution A: The above polyamide in isopropanol at E l XXIII various concentrations given below.

Solution B. Toluene diisocyanate (4% by volume) in Wool top was treated with solutions of various complebenzene. mentary components A and B, using the technique de- Wool swatches were wet-out in Solution A for various scribed in Example I, part 3. The products were tested times (as given below), passed through a squeeze roll, for shrinkage in the following manner: The products were and air-dried at room temperature for one hour to remove gilled to remove any fiber-to-fiber bonding which may solvent. The dried swatches were then dipped in Solution have occurred during treatment. The products were then B at room temperature for one minute, passed through a cut to standard length (50 cm.), sewn into a casing of squeeze roll, hand washed and air-dried. Shrinkage tests cheesecloth, and given a 15-minute wash in an agitatoron the products and a control sample (whereon the treat- 0 type household washing machine. After washing and airment with Solution B was omitted) were tested for shrinkdrying, the samples were measured to determine the perage. The results are given below:

Wt. polyamide Immersion time Area shrinkage centage of shrinkage. The components used and the results of the tests are tabulated below:

38 Wool cloth was treated with the above solutions as in Example I, part 3, using the sequence A-B.

The results of tests on the products are given below.

l Extraction with henzeuc, 3 hours in Soxhlet extractor. No'rE.Iucrease in water repellency after extracton and after washing believed due to remov al of unreacted hydrophihc materials from cloth.

PA=Polyamide as described in Ex. XXI in isopropanol.

PU=Polyurethane as described in Ex. X'IX, in methyl chloroform.

Ter=Terpolymer of ethylene, vinyl acetate, and methaerylyl chloride as describedin Ex. I, in methyl chloroform.

TDI=toluene diisocyanate in methyl chloroform.

HMDA=Hexamethylene diamine, in water plus 0.05% non-ionic wetting agent.

Embodiment 5 In accordance with this embodiment, Component A is a polysiloxane. A particular benefit achieved with such copolymers is the imparting to the fibers of a high degree of water repellency and consequently resistance to soils. Generally, the polysiloxane will contain hydroxy or amine radicals as the highly reactive groups and the polymer is preferably applied as a solution (or emulsion) in water. Component B is a compound containing carbonyl halide, sulphonyl halide, haloformate, carbamyl halide, anhydride, or isocyanate groups (the latter being preferred) and is applied as a solution in an essentially water-immisicible solvent such as benzene, toluene, or the like.

This Embodiment 5 of the invention is further illustrated below:

Example XXIV Component A was a commercial polysiloxane containing more than three amino grou s per molecule. This polymer had a specific gravity of .988 to 1.005 at C., viscosity 100 to 400 centistokes and contained 5.5 to 6.3% free NH The repeating unit of the polysiloxane is believed to have the structure Solution A: The above polysiloxane was stirred into water containing added acetic acid to give a pH of about 11 in the resulting milky solution. One solution at a concentration of 3% polysiloxane and another at 1.5% polysiloxane were thus prepared.

Solution B: 2% (by volume) of 2,4-toluene diisocyanate in methyl chloroform.

Having thus described our invention, we claim:

1. Fibrous material carrying a deposit of a polymer cross-linked through reaction with a fixative,

the polymer being a polysiloxane containing reactive groups selected from the class consisting of hydroxy, amine, carbonyl halide, chloroformate and isocyanate groups,

the fixative being a multifunctional compound containing reactive groups complementary to those of the polymer and selected from the class consisting of carbonyl halide, sulphonyl halide, haloformate, carbamyl halide, anhydride, imide, amine, imine, hydroxy, and isocyanate,

said product being produced by serially impregnating a fibrous material with two solutions, one solution containing in a first solvent the said polymer, the other solution containing in a second solvent the said fixative, the first and second solvents being substantially mutually immiscible, the polymer directly crosslinking with the fixative under said conditions to form a three-dimensional polymer on the fibrous material.

2. Fibrous material carrying a deposit of a polymer cross-linked throng-h reaction with a multifunctional isocyanate fixative,

the polymer being a polysiloxane containing free amine groups,

said product being produced by serially impregnating a fibrous material with two solutions, one solution containing in a first solvent the said polymer, the other solution containing in a second solvent the said fixative, the first and second solvents being substantially mutually immiscible, the polymer directly crosslinking with the fixative under said conditions to form a three-dimensional polymer on the fibrous material.

3. The product of claim 2 wherein the fibrous material is wool and wherein the said deposit is chemically bonded thereto.

References Cited UNITED STATES PATENTS 5/1954 Cuprey et a1 8127.6 X 2/1963 Miller et al 8-128 

1. FIBROUS MATERIAL CARRYING A DEPOSIT OF A POLYMER CROSS-LINKED THROUGH REACTION WITH A FIXATIVE, THE POLYMER BEING A POLYSILOXANE CONTAINING REACTIVE GROUPS SELECTED FROM THE CLASS CONSISTING OF HYDROXY, AMINE, CAARBONYL HALIDE, CHLOROFORMATE AND ISOCYANATE GROUPS, THE FIXATIVE BEING A MULIFUNCTIONAL COMPOUND CONTAINING REACTIVE GROUPS COMPLEMENTARY TO THOSE OF THE POLYMER AND SELECTED FROM THE CLASS CONSISTING OF CARBONYL HALIDE, SULPHONYL HALIDE, HALOFORMATE, CARBAMYL HALIDE, ANHYDRIDE, IMIDE, AMINE, IMINE, HYDROXY, AND ISOCYANATE, SAID PRODUCT BEING PRODUCED BY SERIALLY IMPREGNATING A FIBROUS MATERIAL WITH TWO SOLUTIONS, ONE SOLUTION CONTAINING IN A FIRST SOLVENT THE SAID POLYMER, THE OTHER SOLUTION CONTAINING IN A SECOND SOLVENT THE SAID FIXATIVE, THE FIRST AND SECOND SOLVENTS BEING SUBSTANTIALLY MUTUALLY IMMISCIBLE, THE POLYMER DIRECTLY CROSSLINKING WITH THE FIXATIVE UNDER SAID CONDITIONS TO FORM A THREE-DIMENSIONAL POLYMER ON THE FIBROUS MATERIAL. 